CN108667426A - Carrier dynamics process measurement device applied to photovoltaic device - Google Patents
Carrier dynamics process measurement device applied to photovoltaic device Download PDFInfo
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- CN108667426A CN108667426A CN201810750349.5A CN201810750349A CN108667426A CN 108667426 A CN108667426 A CN 108667426A CN 201810750349 A CN201810750349 A CN 201810750349A CN 108667426 A CN108667426 A CN 108667426A
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- 238000012545 processing Methods 0.000 claims abstract description 22
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- 239000002096 quantum dot Substances 0.000 claims description 14
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S50/00—Monitoring or testing of PV systems, e.g. load balancing or fault identification
- H02S50/10—Testing of PV devices, e.g. of PV modules or single PV cells
- H02S50/15—Testing of PV devices, e.g. of PV modules or single PV cells using optical means, e.g. using electroluminescence
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses a kind of carrier dynamics process measurement devices applied to photovoltaic device, including spectroscope, the first optical parametric amplifier, the second optical parametric amplifier, pump light processing module, exciting light processing module, photovoltaic device and measurement module；One ultra-short pulse lasers are divided into two bundles by spectroscope, wherein a ultra-short pulse lasers are converted into the pump light of a branch of visible light wave range by the first optical parametric amplifier, the beam pump light is by pump light processing module into focusing on photovoltaic device after line delay, decaying and polarization manipulation, an other ultra-short pulse lasers are converted into the exciting light of a branch of near infrared band by the second optical parametric amplifier, which focuses on after carrying out frequency reducing, decaying and polarization manipulation by exciting light processing module on photovoltaic device.Device using the present invention can realize the measurement of electric charge capture dynamic process, have many advantages, such as that temporal resolution is high, tunable, applied widely.
Description
Technical field
The invention belongs to carrier ultra-fast dynamics field of measuring technique, and in particular to a kind of load applied to photovoltaic device
Flow subdynamics process measurement device.
Background technology
For Colloidal Quantum Dots (such as CdSe, CdS, PbSe and PbS) because of quantum size effect, energy gap is adjustable, and is prepared into
This is low, colloid chemistry methods can be utilized to synthesize in the solution, and is widely paid close attention to.In addition, drawing since bulk is limited
Play strong carrier interaction, quantum dot caused to show the physical process of many novelty, such as ultrafast Auger effect with
Carrier multiplication effect.Wherein, the energy gap of PbS quantum is 0.41eV, can be used for photovoltaic device and expands luminous sensitivity
To near infrared band.By optimizing the ligand of quantum-dot structure and quantum dot surface, the Photovoltaic Device Performance based on the quantum dot
Although being increased dramatically, electricity conversion still very it is low (<10%).Therefore, no matter from commercial or scientific research angle
Degree, the performance of photovoltaic device still need to further be promoted.In order to reach this target, material property and carrier prisoner is expressly understood
It is most important to obtain mechanism.
Limitation electricity conversion a key factor be from active layer extract charge efficiency it is low.Quantum dot surface is deposited
A large amount of defects, be easy to form the surface state of local.These defect states can capture photo-generated carrier as trapping centre, drop
The mobility of low charge increases compound probability, thus which limits the thickness of device and the efficiency of light absorption.Therefore,
Control key factor of the concentration of quantum dot surface defect with depth at raising electricity conversion.
Charge generates, capture and recombination process occur at different times on scale, after typically occurring in light excitation
Within several nanoseconds (ns).At present in material carrier generate, the research of the ultrafast process such as transition and relaxation, mainly pumped using femtosecond
The method of Pu-detection.The laser pulse of one beam intensity causes the variation of material character with laser as pump light；It is a branch of weak
Laser pulse as detection light, for detecting pump light caused by change of properties.Light beam is obtained by change in location spatially
Delay in time.Change the distance of optical delay line so that have different time delays between pump light and detection light, survey
Strength Changes after amount detection light permeable material.The Strength Changes reflect the relaxation process of excitation state carrier in material.
The relationship of luminous intensity and time delay is detected by foundation, so that it may to obtain the time resolution process of carrier transition and relaxation.
The wavelength for detecting light and pump light can be different, can be divided into monochromatic, double-colored or polychrome pump probe.
It is newest studies have shown that the carrier of the carrier and capture of quantum dot transient absorption process and movement is all related
System, the image tested is a coefficient result.In addition to microwave and THz wave (THz) can detect local photoelectricity
Outside leading, pure optical means can neither distinguish free carrier and bound charge, can not provide spectrum observation amount and device
The direct relation of performance.On the other hand, pump probe technology is more demanding to photovoltaic device, for example photovoltaic device is required to have one
Fixed translucency, and significantly scattering etc. cannot occur through the detection light beam of photovoltaic device.In most cases, when amount
After son point is packaged into photovoltaic device, pumping-detection technology is no longer applicable in.Therefore, it is badly in need of designing a suitable photovoltaic device
Carrier dynamics process measurement device.
Invention content
The technical issues of must not measuring electric charge capture dynamic process in photovoltaic device for solution, the present invention provides one kind and answers
For the carrier dynamics process measurement device of photovoltaic device, the measurement of electric charge capture dynamic process can be realized.
To achieve the above object, technical solution of the present invention is as follows：
A kind of carrier dynamics process measurement device applied to photovoltaic device is characterized by：Including spectroscope,
One optical parametric amplifier, the second optical parametric amplifier, pump light processing module, exciting light processing module, photovoltaic device and
Measurement module；One ultra-short pulse lasers are divided into two bundles by spectroscope, wherein a ultra-short pulse lasers are by the first optical parameter
Amplifier is converted into the pump light of a branch of visible light wave range, the beam pump light by pump light processing module into line delay, decaying and
It is focused on photovoltaic device after polarization manipulation, and background current I is obtained by measurement module measurement, in addition a ultra-short pulse lasers
The exciting light of a branch of near infrared band is converted by the second optical parametric amplifier, the beam exciting light by exciting light processing module into
It is focused on photovoltaic device after row frequency reducing, decaying and polarization manipulation, and is measured and obtained after measuring background current I by measurement module
Signal code I1, wherein pump light is reached earlier than exciting light on photovoltaic device.
Using the above structure, it is seen that on the photovoltaic device that can be worked, generation freely carries for the pump light irradiation of optical band
Stream and capture carrier, free carrier form a reference current, i.e. background current I；After a time delay, close red
The exciting light of wave section irradiates same photovoltaic device, and the electrons and holes generated by pump light are absorbed, therefore is carried to them
Additional energy is supplied, if these carriers are free carriers, their dynamic process will not be by these additional energy
The influence of amount, it will return quickly to the state before excitation, if these are the charges captured by shallow energy level, additional energy energy
Enough make carrier go to capture, therefore provides additional signal code I for photovoltaic device1；Adjust prolonging for pump light processing module
When the time, time delay of the exciting light with respect to pump light can be changed, obtain the current signal of different moments, it is hereby achieved that
I1/ I with delay time relationship, and then obtain carrier capture and go capture dynamic process, wherein normalized I1/
I reflections are the relative quantities that state is captured in device.
As preferred：The pump light processing module includes being successively set on the first optical parametric amplifier and photovoltaic device
Between delay component, half-wave plate, the first polarizing film and the first condenser lens.It using the above structure, can be with by being delayed component
Time delay of the exciting light with respect to pump light is controlled, can be decayed pump light in conjunction with the first polarizing film by half-wave plate, by the
One polarizing film can be along the polarization of determining pump light, and then can pump light be focused on photovoltaic device by the first condenser lens
On.
As preferred：The hollow retroreflector that the delay component includes translation stage and is arranged on translation stage, it is described hollow
Retroreflector is between the first optical parametric amplifier and half-wave plate.Using the above structure, translation stage uses high-precision flat moving stage,
The time delay of pump light relative excitation light, operation can be accurately controlled by adjusting position of the hollow retroreflector on translation stage
It is convenient, it is easy to accomplish.
As preferred：First optical parametric amplifier is broadband non-colinear femtosecond optical parametric amplification device, the half-wave
Piece is broad band half wave piece.Using the above structure, energy after broadband non-colinear femtosecond optical parametric amplification device is irradiated by ultra-short pulse laser
The pump light of visible light wave range is enough generated, and broad band half wave piece can then play pump light the effect of decaying in conjunction with the first polarizing film
Fruit.
As preferred：The exciting light processing module includes being successively set on the second optical parametric amplifier and photovoltaic device
Between optical attenuator, chopper, the second polarizing film and the second condenser lens.It using the above structure, can by chopper
The repetition rate for accurately controlling exciting light can be decayed exciting light by optical attenuator, can be along determination by the second polarizing film
The polarization of exciting light, and exciting light can then be focused on photovoltaic device by the second condenser lens
As preferred：It is provided with aperture between second polarizing film and the second condenser lens.Using the above knot
Structure can filter out interference laser.
As preferred：Second optical parametric amplifier is near infrared band femtosecond pulse optical parametric amplifier, institute
It is light-balancing filter to state optical attenuator.Using the above structure, near infrared band femtosecond pulse optical parametric amplifier is by ultrashort
The exciting light of near infrared band can be generated after pulsed laser irradiation, the high intensity that light-balancing filter can bear exciting light is shone
It penetrates, and effective attenuation exciting light.
As preferred：The photovoltaic device includes in layer structure and the glassy layer being bonded successively, transparent electrode layer, hole
Transport layer, quantum dot light-absorption layer, hole blocking layer and electron transfer layer are provided with metal electrode in the electron transfer layer,
In, the quantum dot light-absorption layer is PbS quantum layers.Using the above structure, the energy gap of PbS quantum is 0.41eV, can be used
Luminous sensitivity is extended near infrared band in photovoltaic device, manufacturing cost is low.
As preferred：The measurement module includes low-noise current amplifier and lock-in amplifier, the low-noise current
The input terminal of amplifier is electrically connected with transparent electrode layer and metal electrode respectively, the output end and lock of the low-noise current amplifier
Phase amplifier is electrically connected.Using the above structure, the electric current that photovoltaic device generates is after the amplification of low-noise current amplifier by locking phase
Amplifier is amplified measurement.
Compared with prior art, the beneficial effects of the invention are as follows：
Using the carrier dynamics process measurement device provided by the invention applied to photovoltaic device, swashed by pumping-
The mode of hair measure transient photocurrents obtain photovoltaic device in bound charge information, can under photovoltaic device working condition into
Row measures, without carrying out decomposition experiment；By changing the opposite polarization direction of pump light and exciting light, different polarization can be obtained
Time resolution electric current under configuring condition, to obtain the anisotropic parameters of photovoltaic device；Measurement Resolution can be according to survey
Amount demand different adjustment；Also, it is applied widely, it is applicable not only to photovoltaic device, is also applied for other similar active devices；
Therefore, the present invention has many advantages, such as that temporal resolution is high, tunable, applied widely.
Description of the drawings
Fig. 1 is the structural diagram of the present invention；
Fig. 2 is the sectional view of photovoltaic device.
Specific implementation mode
The invention will be further described with attached drawing with reference to embodiments.
As shown in Figure 1, a kind of carrier dynamics process measurement device applied to photovoltaic device, including spectroscope 1,
One optical parametric amplifier 2, the second optical parametric amplifier 12, pump light processing module, exciting light processing module, photovoltaic device
23 and measurement module.
Fig. 1 is referred to, the pump light processing module includes being successively set on the first optical parametric amplifier 2 and photovoltaic device
Delay component, half-wave plate 9, the first polarizing film 10 between part 23 and the first condenser lens 11.Wherein, first optical parameter
Amplifier 2 is broadband non-colinear femtosecond optical parametric amplification device (referring to Chinese patent CN200610105338.9), and the broadband is non-
Conllinear femtosecond optical parametric amplification device can generate the pump light of visible light wave range by incident ultra-short pulse laser.The delay
Component includes translation stage 4 and the hollow retroreflector 5 that is arranged on translation stage 4, and the translation stage 4 uses high-precision flat moving stage,
Precision is better than 1um, and the hollow retroreflector 5, can be in translation stage 4 between the first optical parametric amplifier 2 and half-wave plate 9
Control under move, change optical path length, to control the delay time of pump light.The half-wave plate 9 is broad band half wave piece, energy
The high intensity illumination for enough bearing pump light plays the effect of decaying in conjunction with the first polarizing film 10 and to pump light.Described first partially
The piece 10 that shakes is used to determine the polarization of pump light.First condenser lens 11 is used to pump light focusing on photovoltaic device 23.
Further, the first speculum 3 is provided between first optical parametric amplifier 2 and hollow retroreflector 5,
The pump light that first optical parametric amplifier 2 generates is reflected into through the first speculum 3 in hollow retroreflector 5.In the middle backlash
The second speculum 6, third speculum 7 and the 4th speculum 8 being arranged in order are provided between emitter 5 and half-wave plate 9, from hollow
The pump light directive half-wave plate 9 after the second speculum 6, third speculum 7 and the 4th speculum 8 successively that retroreflector 5 is emitted.It is logical
The control of pumping light transmission path and time can be convenient for by crossing these speculums, simple and reliable, easily operated.
Fig. 1 is referred to, the exciting light processing module includes being successively set on the second optical parametric amplifier 12 and photovoltaic
Optical attenuator 14, chopper 15, the second polarizing film 18, aperture 19 between device 23 and the second condenser lens 20.Its
In, second optical parametric amplifier 12 is near infrared band femtosecond pulse optical parametric amplifier, which flies
Pulse per second (PPS) optical parametric amplifier is used to generate the exciting light of near infrared band.The optical attenuator 14 is light-balancing filter,
Intensity for adjusting exciting light.The chopper 15 and is electrically connected for changing the repetition rate of laser with lock-in amplifier 21
It connects.Second polarizing film 18 is used to determine the polarization of exciting light.The aperture 19 can filter out interference laser.Described
Two condenser lenses 20 are used to exciting light focusing on photovoltaic device 23.
Further, it is provided with the 5th speculum between second optical parametric amplifier 12 and optical attenuator 14
13, the exciting light that the second optical parametric amplifier 12 generates is reflected into through the 5th speculum 13 on optical attenuator 14.Described
The 6th speculum 16 and the 7th speculum 17 being arranged in order are provided between chopper 15 and the second polarizing film 18, from chopper
Exciting lights the second polarizing film of directive 18 after the 6th speculum 16 and the 7th speculum 17 successively of 15 outgoing.Pass through these reflections
Mirror can be convenient for the control of excitation light transmission path and time, simple and reliable, easily operated.
Fig. 2 is referred to, the photovoltaic device 23 includes in layer structure and the glassy layer 231 being bonded successively, transparent electrode
Layer 232, hole transmission layer 233, quantum dot light-absorption layer 234, hole blocking layer 235 and electron transfer layer 236 are passed in the electronics
Defeated layer 236 is provided with metal electrode 237.Wherein, the transparent electrode layer 232 uses ITO electro-conductive glass；The hole transmission layer
233 be the PEDOT being deposited on ito transparent electrode:PSS hole transmission layers, thickness are preferably 50nm；The quantum dot light-absorption layer
234 be PbS quantum layers, is prepared by spray coating method, thickness is preferably 10um, and thickness can change according to actual conditions；The hole
Barrier layer 235 uses PCBM materials, and thickness is preferably 100nm, and PbS quantum layers are attached to by the way of depositing in air
On；The electron transfer layer 236 is ZnO materials, and thickness is preferably 40nm, is equally attached to by the way of depositing in air
On hole blocking layer 235；The metal electrode 237 is Au materials, and thickness is preferably 80nm, by vapor deposition in vacuum evaporation instrument
It goes.
Refer to Fig. 1 and Fig. 2, the measurement module includes low-noise current amplifier 22 and lock-in amplifier 21, described
The input terminal of low-noise current amplifier 22 is electrically connected with transparent electrode layer 232 and metal electrode 237 respectively, the low-noise current
The output end of amplifier 22 is electrically connected with lock-in amplifier 21.Specifically, the photovoltaic device 23 can be generated through light irradiation
Photoelectric current, side of the glassy layer 231 far from transparent electrode layer 232 is towards incident laser, in the transparent electricity of photovoltaic device 23
Extraction wire is connect with low-noise current amplifier 22 respectively on pole layer 232 and metal electrode 237, and the electric current of generation is through low noise
Current amplifier 22 amplifies, and is then attached to lock-in amplifier 21 and is amplified measurement.
Further, all of above device is all placed on optical table 24, to ensure the installation convenient for each device, adjust
Section and use.
Working principle of the present invention is as follows：
The pump light of visible light wave range irradiates on photovoltaic device 23, generates free carrier and capture carrier, wherein
Free carrier forms a reference current, that is, above-mentioned background current I；After a time delay, near infrared band
Exciting light irradiate on photovoltaic device 23, the electrons and holes generated by pump light are absorbed, therefore are provided to them
Additional energy, if these carriers are free carriers, their dynamic process will not be by these additional energies
It influences, it will return quickly to the state before excitation, if these are the charges captured by shallow energy level, additional energy can make
Carrier goes to capture, and additional signal code I is provided for photovoltaic device 231.By changing hollow retroreflector 5 on translation stage 4
Position, that is, change the time delay between exciting light and pump light, the current signal of different moments can be obtained, thus
We can obtain I1/ I with delay time relationship, and then obtain carrier capture and go capture dynamic process.Its
In, normalized I1/ I reflections are the relative quantities that state is captured in device.
The measurement of the above electric current all carries out in a short-circuit situation, that is, without additional power source.Wherein, background current
The measurement of I：In the case of no exciting light, only with pump light carry out irradiation photovoltaic device 23, connection lock-in amplifier 21 into
Row measures.Signal code I1Measurement：Pump light and exciting light irradiate photovoltaic device 23 simultaneously, are carried out using lock-in amplifier 21
It measures.
The course of work of the present invention is as follows：
One ultra-short pulse lasers are divided into two bundles by spectroscope 1, wherein a ultra-short pulse lasers are by the first optical parameter
Amplifier 2 is converted into the pump light of a branch of visible light wave range, the beam pump light by pump light processing module into line delay, decaying and
It is focused on after polarization manipulation on photovoltaic device 23, and background current I is obtained by measurement module measurement, in addition a branch of ultrashort pulse swashs
Light is converted into the exciting light of a branch of near infrared band by the second optical parametric amplifier 12, and the beam exciting light is by excitation light processing mould
Block focuses on after carrying out frequency reducing, decaying and polarization manipulation on photovoltaic device 23, and obtains signal code I by measurement module measurement1,
Wherein, pump light is reached earlier than exciting light on photovoltaic device 23.
It should be pointed out that the first condenser lens 11 and the second condenser lens 20 can focus on pump light and exciting light
The same position on photovoltaic device 23, focal spot radius are preferably 50um.The energy ratio of pump light and exciting light is preferably 1:
1000.Also, by the opposite polarization direction for changing pump light and exciting light, that is, use different configuration of first polarizing film, 10 He
Second polarizing film 18 can obtain the time resolution electric current under different polarization configuring condition, to obtain each of photovoltaic device 23
Anisotropy parameter.In the present embodiment using the opposite polarization direction of pump light and exciting light be 54 °, can obtain at this time not
There is the excitation state dynamic information of molecularly oriented effects.The repetition rate of pumping laser is preferably 1kHz, the frequency of exciting light
Rate is adjusted by chopper 15, is preferably arranged to 400Hz.
Finally, it should be noted that foregoing description is only the preferred embodiment of the present invention, the ordinary skill people of this field
Member under the inspiration of the present invention, without prejudice to the purpose of the present invention and the claims, can make table as multiple types
Show, such transformation is each fallen within protection scope of the present invention.
Claims (9)
1. a kind of carrier dynamics process measurement device applied to photovoltaic device, it is characterised in that：Including spectroscope (1),
First optical parametric amplifier (2), the second optical parametric amplifier (12), pump light processing module, exciting light processing module, light
Lie prostrate device (23) and measurement module；
One ultra-short pulse lasers are divided into two bundles by spectroscope (1), wherein a ultra-short pulse lasers are put by the first optical parameter
Big device (2) is converted into the pump light of a branch of visible light wave range, the beam pump light by pump light processing module into line delay, decaying and
It is focused on after polarization manipulation on photovoltaic device (23), and background current I is obtained by measurement module measurement, in addition a branch of ultrashort pulse
Laser is converted into the exciting light of a branch of near infrared band by the second optical parametric amplifier (12), and the beam exciting light is by exciting light
Reason module focuses on after carrying out frequency reducing, decaying and polarization manipulation on photovoltaic device (23), and obtains signal by measurement module measurement
Electric current I1, wherein pump light is reached earlier than exciting light on photovoltaic device (23).
2. the carrier dynamics process measurement device according to claim 1 applied to photovoltaic device, it is characterised in that：
The pump light processing module includes the delay being successively set between the first optical parametric amplifier (2) and photovoltaic device (23)
Component, half-wave plate (9), the first polarizing film (10) and the first condenser lens (11).
3. the carrier dynamics process measurement device according to claim 2 applied to photovoltaic device, it is characterised in that：
The delay component includes the hollow retroreflector (5) of translation stage (4) and setting on translation stage (4), the hollow retroreflector (5)
Between the first optical parametric amplifier (2) and half-wave plate (9).
4. the carrier dynamics process measurement device according to claim 2 or 3 applied to photovoltaic device, feature exists
In：First optical parametric amplifier (2) is broadband non-colinear femtosecond optical parametric amplification device, and the half-wave plate (9) is broadband
Half-wave plate.
5. the carrier dynamics process measurement device according to claim 1 applied to photovoltaic device, it is characterised in that：
The exciting light processing module includes the light being successively set between the second optical parametric amplifier (12) and photovoltaic device (23)
Learn attenuator (14), chopper (15), the second polarizing film (18) and the second condenser lens (20).
6. the carrier dynamics process measurement device according to claim 5 applied to photovoltaic device, it is characterised in that：
It is provided with aperture (19) between second polarizing film (18) and the second condenser lens (20).
7. the carrier dynamics process measurement device according to claim 5 or 6 applied to photovoltaic device, feature exists
In：Second optical parametric amplifier (12) is near infrared band femtosecond pulse optical parametric amplifier, the optical attenuator
Piece (14) is light-balancing filter.
8. the carrier dynamics process measurement device according to claim 1 applied to photovoltaic device, it is characterised in that：
The photovoltaic device (23) includes in layer structure and the glassy layer (231) being bonded successively, transparent electrode layer (232), hole biography
Defeated layer (233), quantum dot light-absorption layer (234), hole blocking layer (235) and electron transfer layer (236), in the electron transfer layer
(236) it is provided with metal electrode (237), wherein the quantum dot light-absorption layer (234) is PbS quantum layers.
9. the carrier dynamics process measurement device according to claim 8 applied to photovoltaic device, it is characterised in that：
The measurement module includes low-noise current amplifier (22) and lock-in amplifier (21), the low-noise current amplifier (22)
Input terminal be electrically connected respectively with transparent electrode layer (232) and metal electrode (237), the low-noise current amplifier (22) it is defeated
Outlet is electrically connected with lock-in amplifier (21).
Priority Applications (1)
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